Pesticidal composition and method of preparing same

ABSTRACT

Alkylated aromatic hydrocarbons of 9-13 carbon atoms in one or more of the alkyl moieties are useful as insect control agents in plant crops.

United States Patent 1151 3,686,419

Duyfjes et al. 1451 Aug. 22, 1972 [54] PESTICIDAL COMPOSITION AND METHODOF PREPARING SAME [56] References Cited [72] Inventors: Werner Duyfjes;Willem Maas,'both of Amsterdam, Netherlands 2 6 4 663 I Z STATES PATENTS424/356 ,9, 11194 Staner [731 Assgnee Amman 2,782,111 2/1957 B10111 etal..7l/2.6 New 3,244,727 4/1966 We'il ..260/327 22 Filed: Jan. 21, 1969[21] AppL NOJ 792,813 Przmary Exammer-Albert T. Meyers AssistantExaminer--Frederick E. Waddell Aitorney-Frank R. Trifari [30] ForeignApplication Priority Data Jan. 23, 1968 Netherlands ..6800959 [571ABSTRACT April 5, 1968 Netherlands ..6804903 Alkylated aromatichydrocarbons f 9 13 carbon atoms in one or more of the alkyl moietiesare useful 52 us. 01 ..424/3S6 as insect control agents in plant crops[51] Int. Cl. ..A0ln 9/00 [58] Field of Search ..424/356 11 Claims, NoDrawings PESTICIDAL COMPOSITION AND METHOD OF PREPARING SAME Thisinvention relates to a new and useful pesticidal composition and tomethods of employing the composition to combat insects and mites inplant crops.

It is known that aromatic hydrocarbons which comprise one or more alkylgroups which contain a total of 9-13 carbon atoms per molecule aresuitable solvents for halogenated aryl oxymonocarboxylic acids orderivatives thereof particularly since these hydrocarbons exert astrengthening action on the herbicidal activity of the said halogenatedaryloxymonocarboxylic acids and their derivatives. Particularlyalkylated benzenes having 9-13 carbon atoms would be suitable for thispurpose (US. Pat. Specification No. 2,782,111).

It is also known that certain aromatic and aliphatic hydrocarbons,particularly the so-called tar oils and mineral oils have also beenapplied as such for the control of eggs of insects of red spider mitesin woody crops during the winter season. These solvents have aconsiderable phytotoxic activity which may principally be ascribed tothe aromatic hydrocarbons contained therein so that use during otherseasons is a danger to the plant growth.

According to the invention it has unexpectedly been found that, in spiteof a complete aromatic character, certain alkyl derivatives of benzenesexhibit little or no phytotoxicity in doses which are required forcontrolling insects and red spider mites in the sensitive stages oftheir development.

According to the invention it has been found that alkylated benzeneswhich are liquid at C and the alkyl portions of which contain 8-15carbon atoms exhibit little or no phytotoxic activity but possessexcellent insecticidal and acaricidal properties. Due to thiscombination of properties, these liquids are suitable for the control ofinsects, red spider mites and their stages of development, notably theeggs, during all seasons of the year without the risk of serious damageto the leaves of trees or other plants occurring as a result of thespraying. These liquids are in particular suitable to replace theso-called summer-oils.

In the present application alkylated benzenes are to be under stood tobe alkyl derivatives of benzene, toluene, xylene and mesitylene havingat least one alkyl group of 81 5 carbon atoms. These alkylated benzenesmay be chemically pure compounds but may also be mixtures thereof.Furthermore, the alkyl group may be branched or nonbranched.

Examples of alkylated benzenes that may be employed are:

l-phenylnonane,

isododecyl benzene,

6-benzyl-undecane,

2,4-dimethyl 4-benzyldecane,

2,4-dirnethyl 4-benzylundecane,

l-phenyl dodecane,

2-phenyl dodecane,

3-phenyl dodecane,

4-phenyl dodecane,

S-phenyl dodecane,

6-phenyl dodecane,

l-phenyl tridecane,

2-phenyl-tridecane,

3-phenyl tridecane,

4-phenyl tridecane,

substituted only with an alkyl group of 12 carbon atoms. These compoundsand those technical mixtures produced in the petrochemical industry inwhich the main component is a benzene substituted only with an alkylgroup of 12 carbon atoms are called hereinafter dodecyl benzene.

Alkylated benzenes are generally products from the petrochemicalindustry. The alkyl portion is formed by polymerization of propylene orbutene. Dependent upon the polymerization process a mixture of more orless branched hydrocarbons of different chain length is produced.

A petrochemical product which is very satisfactory according to theinvention is commercially available under the name of Dobane PT12. Thisis an alkyl benzene having a branched side chain and manufactured frompropylene tetrarner and it consists for more than percent of an alkylbenzene the alkyl group of which contains 12 carbon atoms.

In addition the petrochemical industry supplies a number of mixtures ofalkyl benzene compounds which have substantially straight alkyl groups.Of these products which may alternatively be used for the purpose of theinvention may be mentioned: Dobane 83 (X)(number of carbon atoms sidechain (n) 8-13), Dobane JN (X) (n 10-13), Dobane JN, (B) (nl0-13)andDobane O55 (X)(n=1015).

In tests with eggs of red spiders and of various insects it was foundthat an excellently ovicidal activity can be obtained both with pure andtechnical dodecyl benzene. The dosages correspond in broad outline tothe parafiine oils which are more or less refined such as have been usedup till now for this purpose. Furthermore, it was found that thepercentage of survival of the adult red spider and of various kinds ofinsects is surprisingly small after spraying with dodecyl benzene.

Upon spraying seedlings of tomato, Indian cress, dwarf bean, cotton,cucumber, cabbage and beet in pot experiments with undiluted technicaldodecyl benzene (DOBANE PT 12) which was nebulized in quantities whichcorrespond to a dosage of 40 liters/hectare no damage to the leaves ofthe seedlings was found 2 weeks after nebulizing. In the tests of theseedlings of cucumber it was found that the nebulized technical dodecylbenzene does not spread or spreads slightly on the leaves of thecucumber seedlings.

Dodecyl benzene as such may be used for the application of theinvention. It is alternatively possible to use an emulsion of dodecylbenzene and water as a spraying or nebulizing liquid, or a mixture ofdodecyl benzene and a non-phytotoxic diluent for dodecyl benzene, forexample, refined kerosene.

Two methods may be used for preparing an emulsion of dodecyl benzene andwater:

1. The dodecyl benzene is processed to a so-called miscible oil (oremulsifiable concentrate) by means of a non-ionic emulsifier to which ananionic emulsifier may be added, which solution is mixed with water whenbeing used, producing an oil-in-water emulsion;

2. The dodecyl benzene is processed to a so-called flowable paste eitherby means of annon-ionic, an anionic or a cationic emulsifier or mixturesthereof with water, which paste, or"stock emulsion is diluted with waterwhen being used.

The non-ionic emulsifier which is suitable for the preparation of themiscible oil is, for example, an alkylphenyl polyglycolether having 8 to20 moles of ethylene oxide per mol of alkyl phenol, or a polyoxyethyleneether of an aliphatic school having 12 to 20 carbon atoms with the samenumber of ethylene oxide molecules of a polyoxyethylene compound of apartial esterof a polyalcohol for example, glycerine, and an aliphaticcarboxylic acid having 12m 20 carbon atoms.

For the preparation'of the miscible oil of dodecyl benzene theseemulsifiers are mixed, if desired, with anionic emulsifiers which aresoluble in hydrocarbon oils, for example, amine salts of differentalkyl-aryl sulphonic acids such as dodecyl benzene sulphonic acid or thecalcium salt thereof, and petroleum sulphonate (mahogany soaps), fattyacid soaps, for example, ammonium oleate or sodium oleate or abietates,for example, colophony. In general usable miscible oils are obtained ifa total of approximately 5 percent of the emulsifiers mentionedhereinbefore is added to the dodecyl benzene.

For the preparation of a flowable paste of dodecyl benzene the samesubstances as those described above for the preparation of the miscibleoils as nonionic or ionic emulsifiers may be employed. A tetra-alkylammonium halide is suitable as a cationic emulsifier which can be usedinstead of an anionic emulsifier, for example, the dodecyl trimethylammonium chloride compound or an alkyl pyridine chloride, for example,cetyl pyridine chloride.

For the preparation of a flowable paste, for example 75-85 parts byweight of dodecyl benzene are dispersed in 13-23 parts of water to whichhave been added l-5 parts by weight of emulsifier consisting of ananionic or a non-ionic emulsifier or a cationic emulsifier or mixturesthereof. If desired the emulsion contains a stabilizer such as acaseinate, carboxymethyl cellulose of hydroxyethyl cellulose.

If desired the biocidal activity of the dodecyl benzene may be increasedby the addition of a different pesticide either to the dodecyl benzenephase or to the aqueous phase, for example, in a flowable. Suitable asinsecticides are, for example, organo-phosphorus compounds such asparathion, malathion, D.D.V.P., ethione or 0, O-dimethyl-(3-methyl-4-nitrophenyl)- phosphorothioate, and furthermore halogenatedhydrocarbons such as H.C.H., chlordane, lindane, toxophene orcarbamates, for example, carbaryl.

For the control of insects, red spider mites and development stagesthereof on standing crops, a quantity of 3-20 liters per hectare ofalkylated benzene of the invention is suitable. For example, a quantityof 15-20 liters per hectare is used for the dodecyl benzene.

The dodecyl benzene or the aqueous emulsions thereof may be sprayed bothfrom airplanes and with the aid of machines on the ground. According tothe low-volume technique a quantity of 15-20 liters of dodecyl benzenemay suffice for aerial spraying when the liquid is not diluted withother agents, or is mixed. Very satisfactory results may alternativelybe achieved by aen'al spraying with 5-10 liters of dodecyl benzene bydissolving or dispersing a different insecticide or acaricide in theliquid for example, malathion in a ration of, for example, 3 liters ofdodecyl benzene in [-2 liters of malathion.

Aqueous emulsions are alternatively suitable for aerial spraying. Forexample, a miscible oil of dodecyl benzene whichcontains approximately3. percent'of emulsifier is diluted with the same quantity of waterwhereafter the emulsion can be aerially sprayed on the crops in aquantity of 30-40 liters per hectare.

Aqueous emulsions which contain 2 percent of dodecyl benzene may be usedin conventional spraying apparatus, which emulsions are prepared bymixing a miscible oil or a flowable paste of the type describedhereinbefore with the desired quantity of water.

While we have described our invention in connection with specificembodiments and applications, other modifications thereof will bereadily apparent to those skilled in this art without departing from thespirit and scope of the invention as defined in the appended claims.

EXAMPLE 1:

95 gms ofDobane PT12 were mixed with 5 gms of a mixture ofalkylphenolpolyglycolether and calciumdodecyl benzene sulphonate andstirred untill complete homogeneity.

This preparation was dispersed in 4,9 ls of water whereafter thisemulsion was sprayed on citrus trees infected with spider unites tillrun off. The spider mite population was completely controlled and nophytotoxic effects were observed.

EXAMPLE 2:

gms of Dobane JN(X) were emulsified in 20 gms of an aqueous solutionhaving the following composition:

5 percent polyvinylalcohol 3 percent sodium dodecyl benzene sulphonate92 percent water. This emulsion is of the mayonaise type and isphysically a thick white paste; 2,5 parts per weight of this emulsionwere gradually diluted with 97,5 parts per weight of water. This aqueousemulsion was sprayed as a summer spray on apple trees. Complete controlof spider mites was achieved without noticeable phytotoxic effects.

EXAMPLE 3:

80 gms of Dobane. PT12, 5 grns of Ethion (malathion or parathion) and 5grns of amixt ure of alkylphenolpolyglycolether and calcium dodecylbenzene sulphonate were mixed to complete homogeneity and subsequentlydispersed in 10 Is of water. This emulsion was sprayed on citrus tillrun off. Complete control of spider mite population was achieved and novisible phytotoxicity was observed.

What is claimed is:

1. A method of combatting insects and red spider mites in a plant cropcomprising treating said insects and red spider mites with aninsecticidally and acaricidally effective amount of dodecylbenzene.

2. The method of claim 1, wherein the dodecyl benzene is employed in theform of. an aqueous emulsion wherein a minor amount of an emulsifier isof dodecyl benzene are applied per hectare.

7. The method of claim 6, wherein a2 percent aqueous emulsion of dodecylbenzene is sprayed on the crop.

8. The method of claim 5, wherein about 30-40 liters of the emulsion areemployed per hectare.

9. The method of claim 1, wherein the dodecyl benzene is employed in theform of a solution in a nonphytotoxic diluent.

10. The method of claim 9, wherein the diluent is kerosene. a

11. The method of claim 1, wherein in addition an organophosphorus' or ahalogenated hydrocarbon pesti cide is employed with the dodecylbenzene.

2. The method of claim 1, wherein the dodecyl benzene is employed in theform of an aqueous emulsion wherein a minor amount of an emulsifier ispresent.
 3. The method of claim 2, wherein the aqueous emulsion issprayed on the crop.
 4. The method of claim 2, wherein a non-ionicemulsifier is employed.
 5. The method of claim 3, wherein an amount ofthe emulsion is sprayed on the crop such that from 3-20 liters of thedodecyl benzene is applied per hectare.
 6. The method of claim 1,wherein about 15-20 liters of dodecyl benzene are applied per hectare.7. The method of claim 6, wherein a 2 percent aqueous emulsion ofdodecyl benzene is sprayed on the crop.
 8. The method of claim 5,wherein about 30-40 liters of the emulsion are employed per hectare. 9.The method of claim 1, wherein the dodecyl benzene is employed in theform of a solution in a non-phytotoxic diluent.
 10. The method of claim9, wherein the diluent is kerosene.
 11. The method of claim 1, whereinin addition an organophosphorus or a halogenated hydrocarbon pesticideis employed with the dodecylbenzene.